High-functionality polyols for application in polyurethanes (PUs) were prepared by epoxide ring-opening reactions from epoxidized sucrose esters of soybean oil—epoxidized sucrose soyates—in which secondary hydroxyl groups were generated from epoxides on fatty acid chains. Ester polyols were prepared by using a base-catalyzed acid–epoxy reaction with carboxylic acids (e.g., acetic acid); ether polyols were prepared by using an acid-catalyzed alcohol–epoxy reaction with monoalcohols (e.g., methanol). The polyols were characterized by using gel permeation chromatography, FTIR spectroscopy, 1H NMR spectroscopy, differential scanning calorimetry (DSC), and viscosity measurements. PU thermosets were prepared by using aliphatic polyisocyanates based on isophorone diisocyanate and hexamethylene diisocyanate. The properties of the PUs were studied by performing tensile testing, dynamic mechanical analysis, DSC, and thermogravimetric analysis. The properties of PU coatings on steel substrates were evaluated by using ASTM methods to determine coating hardness, adhesion, solvent resistance, and ductility. Compared to a soy triglyceride polyol, sucrose soyate polyols provide greater hardness and range of cross-link density to PU thermosets because of the unique structure of these macromolecules: well-defined compact structures with a rigid sucrose core coupled with high hydroxyl group functionality.